Solid state energy converter

ABSTRACT

A solid-state energy converter with a semiconductor or semiconductor-metal implementation is provided for conversion of thermal energy to electric energy, or electric energy to refrigeration. In n-type heat-to-electricity embodiments, a highly doped n* emitter region made of a metal or semiconductor injects carriers into an n-type gap region. A p-type layer is positioned between the emitter region and gap region, allowing for discontinuity of corresponding Fermi-levels and forming a potential barrier to sort electrons by energy. Additional p-type layers can optionally be formed on the collector side of the converter. One type of these layers with higher carrier concentration (p*) serves as a blocking layer at the cold side of the converter, and another layer (p**) with carrier concentration close to the gap reduces a thermoelectric back flow component. Ohmic contacts on both sides of the device close the electrical circuit through an external load to convert heat to electricity. In the case of a refrigerator, the external load is substituted by an external power supply.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 10/801,072filed Mar. 15, 2005, now U.S. Pat. No. 7,109,408, issued Sep. 19, 2006,which application claims the benefit of priority to U.S. ProvisionalApplication No. 60/454,511, filed on Mar. 13, 2003, and is acontinuation-in-part of U.S. application Ser. No. 10/307,241, filed onNov. 27, 2002, now U.S. Pat. No. 6,906,449, which is a divisional ofU.S. application Ser. No. 09/519,640, filed on Mar. 6, 2000, now PatentNo. U.S. Pat. No. 6,489,704 B1, which claims the benefit of priority toU.S. Provisional Application No. 60/123,900, filed on Mar. 11, 1999, thedisclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the conversion of thermal energy toelectrical energy, and electrical energy to refrigeration, and moreparticularly to a solid state thermionic converter using semiconductordiode implementation.

2. Relevant Technology

Thermionic energy conversion is a method of converting heat energydirectly into electrical energy by thermionic emission. In this process,electrons are thermionically emitted from the surface of a metal byheating the metal and imparting sufficient energy to a portion of theelectrons to overcome retarding forces at the surface of the metal inorder to escape. Unlike most other conventional methods of generatingelectrical energy, thermionic conversion does not require either anintermediate form of energy or a working fluid, other than electricalcharges, in order to change heat into electricity.

In its most elementary form, a conventional thermionic energy converterincludes one electrode connected to a heat source, a second electrodeconnected to a heat sink and separated from the first electrode by anintervening space, leads connecting the electrodes to an electricalload, and an enclosure. The space in the enclosure is either highlyevacuated or filled with a suitable rarefied vapor, such as cesium.

The essential process in a conventional thermionic converter is asfollows. The heat source supplies heat at a sufficiently hightemperature to one electrode, the emitter, from which electrons arethermionically evaporated into the evacuated or rarefied vapor-filledinterelectrode space. The electrons move through this space toward theother electrode, the collector, which is kept at a low temperature nearthat of the heat sink. There the electrons condense and return to thehot electrode via external electrical leads and an electrical loadconnected between the emitter and the collector. The flow of electronsthrough the electrical load is sustained by the temperature differencebetween the electrodes. Thus, electrical work is delivered to the load.

Thermionic energy conversion is based on the concept that a low electronwork function cathode in contact with a heat source will emit electrons.These electrons are absorbed by a cold, high work function anode, andthey can flow back to the cathode through an external load where theyperform useful work. Practical thermionic generators are limited by thework function of available metals or other materials that are used forthe cathodes. Another important limitation is the space charge effect.The presence of charged electrons in the space between the cathode andanode will create an extra potential barrier which reduces thethermionic current. These limitations detrimentally affect the maximumcurrent density, and thus present a major problem in developinglarge-scale thermionic converters.

Conventional thermionic converters are typically classified as vacuumconverters or gas-filled converters. Vacuum converters have an evacuatedmedium between the electrodes. These converters have limited practicalapplications.

Embodiments in a first class of gas-filled converters are provided witha vaporized substance in the interelectrode space that generatespositive ions. This vaporized substance is commonly a vaporized alkalimetal such as cesium, potassium and rubidium. Because of the presence ofthese positive ions, liberated electrons can more easily travel from theemitter to the collector. The emitter temperature in this type ofconventional device is in part determined by the vaporizationtemperature of the substance that generates the positive ions.Generally, the emitter temperature should be at least 3.5 times thetemperature of the reservoir of the positive ion generating substance ifefficient production of ions is to be achieved in these conventionaldevices.

Embodiments in a second class of gas-filled converters are provided witha third electrode to generate ions, and the gas in the interelectrodespace in these conventional devices is an inert gas such as neon, argon,or xenon. Although these converters can operate at lower temperatures,such as about 1500 K, they are more complex.

Typical conventional thermionic emitters are operated at temperaturesranging from about 1400 K to about 2200 K, and thermionic collectors areoperated at temperatures ranging from about 500 K to about 1200 K. Underoptimum conditions of operation, overall efficiencies of energyconversion range from 5% to 40%, electrical power densities are of theorder of 1 to 100 watts/cm², and current densities are of the order of 5to 100 A/cm². In general, the higher the emitter temperature, the higherthe efficiency, the power and current densities with designs accountingfor radiation losses. The voltage at which the power is delivered fromone unit of a typical converter is 0.3 to 1.2 volts, i.e., about thesame as that of an ordinary electrolytic cell. Thermionic systems with ahigh power rating frequently include many thermionic converter unitsconnected electrically in series. Each thermionic converter unit istypically rated at 10 to 500 watts.

The high-temperature attributes of thermionic converters areadvantageous for certain applications, but they are restrictive forothers because the required emitter temperatures are generally beyondthe practical capability of many conventional heat sources. In contrast,typical thermoelectric converters are operable at heat sourcetemperatures ranging from about 500 K to about 1500 K. However, evenunder optimum conditions, overall efficiencies of thermoelectric energyconverters only range from 3% to 10%, electrical power densities arenormally less than a few watts/cm², and current densities are of theorder of 1 to 100 A/cm².

From a physics standpoint, thermoelectric devices are similar tothermionic devices. In both cases a temperature gradient is placed upona metal or semiconductor, and both cases are based upon the concept thatelectron motion is electricity. However, the electron motion alsocarries energy. A forced current transports energy for both thermionicand thermoelectric devices. The main difference between thermoelectricand thermionic devices is in the transport mechanism; ballistic anddiffusive transport for thermionics and ohmic transport forthermoelectrics. Ohmic flow is macroscopically diffusive, but notmicroscopically diffusive. The distinguishing feature is whether excesscarriers are present. In thermoelectrics, the carriers normally presentare responsible for current. In thermionics, the current is due toputting excess carriers in the gap. A thermionic device has a relativelyhigh efficiency if the electrons ballistically go over and across thegap. For a thermionic device all of the kinetic energy is carried fromone electrode to the other. The motion of electrons in a thermoelectricdevice is quasi-equilibrium and ohmic, and can be described in terms ofa Seebeck coefficient, which is an equilibrium parameter.

In structures with narrow barriers, the electrons will not travel farenough to suffer collisions as they cross the barrier. Under thesecircumstances, the ballistic version of thermionic emission theory is amore accurate representation of the current transport.

Solutions to the foregoing problems have been sought according to thepresent state of the art by using vacuum converters or gas-filledconverters. Attempts to reduce space-charge effects with vacuumconverters have involved the reduction of the interelectrode separationto the order of micrometers. Attempts to reduce the same effects withgas-filled converters have led to the introduction of positive ions intothe cloud of electrons in front of the emitter. Nevertheless, theseconventional devices still present shortcomings such as those related tolimited maximum current densities and temperature regimes.

Consequently, there remains a need to provide a more satisfactorysolution to converting thermal energy to electrical energy at lowertemperature regimes with high efficiencies and high power densities.

SUMMARY OF THE INVENTION

The present invention relates to solid state energy converter devicesand methods with a semiconductor or semiconductor-metal implementationfor conversion of thermal energy to electric energy, or electric energyto refrigeration. In n-type heat-to-electricity embodiments of theinvention, a highly doped n* emitter region made of a metal orsemiconductor material injects carriers into an n-type gap region. Ap-type layer is positioned between the emitter region and the gapregion, allowing for discontinuity of corresponding Fermi-levels andforming a potential barrier to sort electrons by energy.

Additional p-type layers can optionally be formed on the collector sideof the gap region. One type of these layers with higher carrierconcentration (p*) serves as a blocking layer at the cold side of thedevice, and another layer (p**) with carrier concentration close to then-type concentration in the gap reduces a thermoelectric back flowcomponent. These p-type layers can be used alone or together on thecollector side. Ohmic contacts on both sides of the device close theelectrical circuit through an external load. In the case of arefrigerator, the external load is substituted by an external powersupply.

In additional embodiments of the invention, p-type converters can beformed, as well as thermal diode stacks. The invention works for holesas well as for electrons. Efficiencies approaching thermodynamic limitcan be achieved with the devices of the invention.

These and other features of the present invention will become more fullyapparent from the following description and appended claims, or may belearned by the practice of the invention as set forth hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to illustrate the manner in which the above recited and otherfeatures of the invention are obtained, a more particular description ofthe invention briefly described above will be rendered by reference tospecific embodiments thereof, which are illustrated in the appendeddrawings. Understanding that these drawings depict only typicalembodiments of the invention and are not therefore to be consideredlimiting in scope, the invention will be described and explained withadditional specificity and detail through the use of the accompanyingdrawings in which:

FIG. 1 is a schematic depiction of a thermal diode embodiment of thepresent invention that improves thermoelectric performance of a givensemiconductor device;

FIG. 2 is a plot of the Fermi level for InSb, relative to the bottom ofthe conduction band, as a function of ionized acceptor concentration(left) and ionized donor concentration (right);

FIGS. 3A and 3B are plots of a calculated carrier concentration impurityprofile and corresponding barrier shape for He-4 implantation;

FIG. 4 is a plot of relative electric output as a function of emitterbarrier height;

FIG. 5 is a plot of the ideal calculated positions of the Fermi-leveland the bottom of the conductance band for a InSb gap region with 10¹⁸cm³ Te doping and a p-type barrier;

FIG. 6 is a plot of relative electric output normalized tothermoelectric performance as a function of a collector barrier height;

FIG. 7 is a plot of the calculated energy levels for an optimizedconverter of the invention having an emitter barrier combined withanother injection barrier;

FIG. 8 is a plot of the calculated energy levels for an optimizedconverter of the invention having an emitter barrier combined with ablocking layer;

FIG. 9 is a plot of the calculated energy levels for an optimizedconverter of the invention having an emitter barrier combined with bothanother injection barrier and a blocking layer;

FIG. 10A is a schematic depiction of a thermal diode converter of theinvention that includes an emitter injection barrier-only stack;

FIG. 10B is a schematic depiction of a further thermal diode converterof the invention that includes an emitter injection barrier pluscompensated layer stack; and

FIG. 10C is a schematic depiction of another thermal diode converter ofthe invention that includes an emitter injection barrier plus collectorinjection barrier stack.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to solid state energy converter deviceswith a semiconductor or semiconductor-metal implementation forconversion of thermal energy to electric energy, or electric energy torefrigeration. The invention can be implemented for holes as well as forelectrons. Efficiencies approaching thermodynamic limits can be achievedwith the devices of the invention.

Referring to the drawings, FIG. 1 is a schematic depiction of oneembodiment of a solid state energy converter of the invention in theform of a thermal diode 10, which improves thermoelectric performance ofa given semiconductor device. As shown in FIG. 1, thermal diode 10 hasn-type conductivity, and includes an emitter region 12 in thermalcommunication with a hot heat exchange surface 14. The emitter region 12comprises an n-type region 16 with donor concentration n* for electronemission. A semiconductor gap region 18, with a donor doping n, is inelectrical and thermal communication with emitter region 12. Ap-typebarrier layer 20 with acceptor concentration p* is interposed betweenemitter region 12 and gap region 18. The barrier layer 20 is configuredto provide a potential barrier and Fermi-level discontinuity betweenemitter region 12 and gap region 18.

As further shown in FIG. 1, thermal diode 10 can optionally include acollector region 22 in thermal communication with a cold heat exchangesurface 24. The gap region 18 is in electrical and thermal communicationwith collector region 22 when present. A first ohmic contact 26 is inelectrical communication with emitter region 12 and a second ohmiccontact 28 is in electrical communication with collector region 22. Thefirst and second ohmic contacts 26, 28 close an electrical circuit 30through an external load (R_(L)) for heat to electricity conversion.Alternatively, the first and second ohmic contacts 26, 28 can closeelectrical circuit 30 through an external power source (PS), in place ofthe external load, for electricity to refrigeration conversion.

The collector region 22 can include an additional injection barrierlayer (p^(I)) with a carrier concentration p** that is adjacent to gapregion 18 to reduce a thermoelectric back flow component. The collectorregion 22 can also include an additional compensation layer (p^(C)),with acceptor concentrations* being the same as donor concentration ingap region 18, and serving as a blocking layer at the cold side of theconverter.

The collector region 22 can also include both p-type layers, theadditional injection layer (p^(i)) and the additional compensation layer(p^(C)), with the injection layer placed between the gap region and thecompensation layer.

It should be understood that emitter region 12 and gap region 18 greatlyimprove thermoelectric performance of thermal diode 10, and the deviceis viable even without collector region 22.

The emitter region 12 is formed of electrically and thermally conductivematerials such as metals, metal alloys, semiconductors, or dopedsemiconductors. The emitter may also include an electrically andthermally conductive material on a substrate. Non-limiting examples ofsuitable materials for the emitter region include Hg_(1-x)Cd_(x)Te,Cd₃As₂, CdSnAs₂, SiGe alloys, TAGS, InAs_(1-x) Sb_(x), Ga_(x)In_(1-x)As_(y)Sb_(1-y), PbTe, PbSe, PbS, Ge_(1-x)Sn_(x) and the like. Theemitter region 12 can have a thickness of greater than about 1 μm, orabout 2 carrier scattering lengths.

The gap region 18 can be formed with semiconductor materials such asInSb, HgCdTe, Cd₃As₂, CdSnAs₂, Ge_(1-x)Sn_(x), CdGeAs₂, InGaSbAs, PbTe,PbS, PbSe, and the like. The semiconductor materials used in the gapregion can be in the form of wafers doped with an n-type impurity suchas tellurium. The gap region 18 can be segmented so that it includes afirst layer of a semiconductor material, and a second layer that reducesheat flow density made of a metal or a different highly n-dopedsemiconductor material.

The semiconductor gap (first layer) in gap region 18 can be as thin asone or more carrier scattering lengths to preserve potential barrierstructure. For example, the semiconductor gap can be at least 1 carrierscattering length wide, and preferably at least 5 carrier scatteringlengths wide. The gap region can have a total thickness of up to about 1mm. Metal materials that may be used in the gap region include Mo,steel, and the like.

The p-type barrier layer 20 can have a thickness of up to about 1 μm,and can be formed by deposition of a semiconductor such as InSb dopedwith a p-type impurity (e.g. Co, Zn, Ge, Mn, Mg, Fe, Cu. Ag, Cr. etc.).As discussed in more detail hereafter, the p* doping concentration ofthe p-type layer relates to the n doping concentration of the gap regionas p_(i)>n_(i)(m*_(p)/m*_(n)), where m*_(p) is the effective mass ofholes, m*_(n) is the effective mass of electrons, and subscript idenotes ionized fraction of carriers at a given temperature.

In an alternative embodiment of a solid state energy converter of theinvention, thermal diode 10 of FIG. 1 can be formed with p-typeconductivity. Such an embodiment includes an emitter region 12 inthermal communication with a hot heat exchange surface, with the emitterregion comprising a p-type region with acceptor concentration p* forhole emission. A semiconductor gap region 18, with a donor doping p, isin electrical and thermal communication with emitter region 12. Ann-type barrier layer 20 with donor concentration n* is interposedbetween emitter region 12 and gap region 18. The p-type thermal diodecan optionally include a collector region 22 in thermal communicationwith a cold heat exchange surface. A first ohmic contact is inelectrical communication with emitter region 12 and a second ohmiccontact is in electrical communication with collector region 22.

The converter devices of the invention can be formed by conventionaldeposition techniques that are typically used to form metallic andsemiconductor layers, which are well known to those skilled in the art.

EXAMPLES

The following examples are provided to illustrate the present invention,and are not intended to limit the scope of the invention.

Example 1 Emitter and Converter Design

In developing the present invention, indium antimonide (InSb) was usedas a model semiconductor material, due to its commercial availability.InSb has one of the highest known electron mobilities and the largestscattering length (0.8 microns at room temperature). On the other hand,the thermal conductivity of InSb is relatively high, resulting in abelow average thermoelectric figure of merit (ZT=0.2 for optimizedconditions). It should be understood that most of the results achievedexperimentally for InSb can be applied for a variety of othersemiconductors with corrections for their properties. However, twoextreme cases where this approach might not work is when the bandgap istoo small (less than k_(B)T, where k_(B) is Boltzmann's constant and Tis absolute temperature), or too large, such that it is difficult tocreate a thermal current induced Fermi-level discontinuity withinreasonable barrier height, such as less than 10 k_(B)T.

Wafers (gap) doped with tellurium (n-type) were used in the presentdesign. Doping level was around 10¹⁸ atoms per cubic centimeter(atoms/cm³). The basic design for an n-type converter is n*/p/n, wheren* is the emitter (can be either metal or semiconductor), p is thebarrier layer, and n is the gap material. A corresponding p-typeconverter layout is p*/n/p, where p* is the emitter, n is the barrierlayer, and p is the gap material. For simplicity, p-type converterembodiments will not be discussed further, with the understanding thatthe physics involved is the same and design changes are evident. On thecollector side of the converter, addition of a p-type compensation layerfurther improves device performance. An additional current injectioneffect, which is described hereafter, can provide even higher deviceperformance.

In forming a converter according to the present invention, an emitterlayer with an n* region was formed by depositing an InSb layer that washighly doped with tellurium, or by depositing a metal layer in the formof In, Mo, or In—Ga eutectic. The p-type layer was formed to create apotential barrier for hot electron injection, and provides adiscontinuity of the Fermi level, thus preventing electrical short-outof the emitter. Addition of any p-type layer on an n-type gap creates apotential barrier, but only high enough concentration of p-type carriersensures a discontinuity of the Fermi level. In other words, the p-typelayer functions as a separator. Positioning of the Fermi level relativeto the bottom of the conduction band as a function of donor and acceptorconcentration is described by Kane's diagram. FIG. 2 is a Kane's diagramfor InSb, which shows a plot of the Fermi level (meV) as a function ofionized acceptor concentration (left) and ionized donor concentration(right). FIG. 2 illustrates the results for temperatures of 300 K, 350K, 400 K, 450 K, 500 K, 550 K, and 600 K.

The p-type layer was formed using a method based on the fact that avacancy in InSb forms a p-type impurity with the same ionization energyas Te (50 meV). This is convenient in the sense that relativeconcentration of both n- and p-type impurities stays the same over thewhole temperature change range. Vacancy concentration induced by inertgas implantation was modeled by TRIM-91 software (Ziegler and Biersack,IBM, 1991). FIG. 3A is a plot of a calculated carrier concentrationimpurity profile after 20-350 keV ⁴He implantation in InSb doped with Teto 1×10¹⁸ cm⁻³, and FIG. 3B is a corresponding calculated barrier shapefor implantation at room temperature.

This particular impurity profile and others were realized usingcommercial implanters (Core Systems, Inc., Sunnyvale, Calif.). ImplantedInSb wafers were cut into small pieces, typically a few squaremillimeters, and tested in test apparatus, described elsewhere (seee.g., P. Hagelstein and Y. Kucherov, Proceedings of the 2001 FallMaterials Research Society Conference, Boston, Mass., edited by G. S.Nolas, Vol. 691, pp. 319-324, which is incorporated herein byreference). Pieces of the same wafers without ion implanted layersprovided a thermoelectric reference. Cumulative test results are shownin FIG. 4 for 0.5 mm thick wafers in a plot of relative electric outputas multiple of thermoelectric performance for different emitter barrierheights and temperatures.

The barrier width was the same as shown in FIG. 2. The peak ofperformance was approximately one k_(B)T wide (k_(B) is Boltzmann'sconstant and T is the absolute temperature). At 313 K there is no changerelative to the thermoelectric performance, until the barrier heightreaches approximately 4 k_(B)T. Optimum barrier height goes down as thetemperature goes up. There was up to 6 times the thermoelectric outputobserved.

The effective mass of electrons is m*_(n)=m_(n)/m_(o)=0.0136 (m_(o) isfree electron mass), and the effective mass for holes ism*_(p)=m_(p)/m_(o) is 0.2 (see G. Slack, CRC Handbook ofThermoelectrics, p. 420, CRC press, 1995). The ratio is 14.7 andexperimental peak performance occurs when hole concentration is about14.5-15.5 times higher than electron concentration. In other words,Fermi level discontinuity and for this particular case maximum outputhappens when there is a delocalized compensation layer. It should benoted that at low doping levels in the gap, maximum performance can beat barrier doping levels higher than the compensation level to provide ahigher barrier. But in most cases compensation condition is sufficient.In Patent No. U.S. Pat. No. 6,396,191 B1, the disclosure of which isincorporated herein by reference, maximum collector performance at alocalized compensation point is described, when concentration of p andn-type impurities is the same.

In the general case, localized compensation can be written for a givensemiconductor as:p_(i)=n_(i)  (1),where p_(i) is the ionized acceptor impurity concentration and n_(i) isthe ionized donor impurity concentration. Ionized fraction of impurityis defined (for acceptors as an example) as p_(i)=p/(1+gexp−{E_(F)−E_(i)/k_(B)T}, where E_(i) is the ionization energy for agiven impurity, E_(F) is the Fermi level, g is the degeneration factor,which is 4 in the case of InSb, k_(B) is the Boltzmann constant, and Tis the absolute temperature. For a delocalized compensation,corresponding to a maximum emitter performance:p _(i) >n _(i)(m* _(p) /m* _(n))  (2).

Equation (2) allows one to optimize the emitter side for InSb andprobably any other semiconductor. A six times increase in thermoelectricperformance elevates an InSb device to a status of a relatively goodthermoelectric. Ideal calculated positions of the Fermi-level and thebottom of conductance band for an InSb gap with 10¹⁸ cm⁴ Te doping and ap-type barrier are shown in the plot of FIG. 5.

A layer of intrinsic material with a thickness larger than thescattering length functionally appears to be the same as a localizedcompensation layer and can be regarded as an alternative formanufacturing. In this case, an n-type converter will look liken*/i/n/i*, where n* is the emitter, i is the emitter intrinsic layer, nis the gap material and i* is the collector intrinsic layer. It isunderstood that in some cases a combination of both localized anddelocalized barriers might be preferable.

If more efficient materials are started with, for example,Hg_(1-x)Cd_(x)Te, Cd₃As₂, CdSnAs₂, SiGe alloys, TAGS, InAs_(1-x) Sb_(x),Ga_(x)In_(1-x) As_(y)Sb_(1-y), etc., efficiencies approachingthermodynamic limit can be achieved. A 40% of ideal Carnot cycle wasobserved experimentally with Hg_(0.86)Cd_(0.14)Te with In-doped emitter,but even this number can be improved. An actual device for highertemperature operation would require a thin diffusion barrier layer,thinner than the tunnelling length of the carrier in a barrier material,on the emitter interface, to prevent concentration profile wash-out.Known diffusion barriers are typically made of refractory materials likeTiN, ZrN, HfN, TaN, W, etc. In the case of HgCdTe, a known diffusionbarrier material is Yb (ytterbium oxide).

Example 2 Collector Design

The same implantation method was used to study effects of barrier heighton the collector side of a converter. Experimental results are shown inthe plot of FIG. 6, in the form of electric output normalized tothermoelectric performance as a function of a collector barrier height.The collector temperature (T_(c)) was close to the room temperature. Twoseparate effects can be observed. At low barrier height one peak isaround localized compensation, where concentration of a p-type impurityequals an n-type impurity concentration. For this case, ionizationenergy for donors and acceptors is the same. At higher barrier heightsthe second peak position is exactly the same as in FIG. 4, forcorresponding temperatures, suggesting that there is current injectionfrom the gap into the collector contact. Once again, this peakcorresponds to a delocalized compensation layer. The emitter andcollector are separated by a semiconductor layer, which is many timesthicker than both the emitter and collector layer thicknesses. As aresult, it is reasonable to assume that emitter and collector sides workto a large extent independently, at least in the limit when open circuitvoltage across the converter is smaller than both barrier heights. Thisprovides the opportunity to combine the emitter barrier with anotherinjection barrier, with a blocking layer, or with both.

For example, FIG. 7 is a plot of the calculated energy levels for anoptimized converter having an emitter barrier (InSb gap region with 1018cm³ Te doping and thickness of 0.5 mm) combined with another injectionbarrier. The emitter hot side temperature T_(hot)=300° C., and thecollector cold side temperature T_(cold)=10° C. FIG. 8 is a plot of thecalculated energy levels for an optimized converter having an emitterbarrier (InSb gap region with 10¹⁸ cm⁻³ Te doping and thickness of 0.5mm) combined with a blocking layer. The emitter hot side temperatureT_(hot)=300° C., and the collector cold side temperature T_(cold)=10° C.FIG. 9 is a plot of the calculated energy levels for an optimizedconverter having an emitter barrier (InSb gap region with 10¹⁸ cm⁻³ Tedoping and thickness of 0.5 mm) combined with both another injectionbarrier and a blocking layer. The emitter hot side temperatureT_(hot)=300° C., and the collector cold side temperature T_(cold)=10° C.

Barrier heights can be obtained from experimental graphs on FIGS. 4 and6. The same barrier heights can also be obtained using Kane's diagram(see FIG. 1) with formula (1) for a collector blocking layer and formula(2) for emitter and collector injection layers. Correspondingenhancement of thermoelectric performance (in the limit that opencircuit voltage is below the corresponding barrier height) can be ashigh as about 9 in the case of the collector injection layer, about 8 inthe case of a blocking layer, or about 14, when all these layers arepresent.

For thinner plates, enhancement of thermoelectric performance can beeven more dramatic, because thermoelectric open circuit voltage is lowerand does not interfere with collector barrier(s). All performanceenhancements for 0.5 mm thick plates (gap) comes from two thin layerswith combined thickness 300 times less than the gap itself. After a hotcarrier crosses the barrier it propagates in a gap and scatters. Afterroughly 5-10 scatterings the hot carrier is completely thermalized andcarrier distribution in the gap is back to the unperturbedFermi-distribution. For InSb, scattering length is approximately 0.8microns at room temperature, meaning that after 4-8 microns the gap isnot contributing much to the device performance.

If a stack of multiple devices is made and contact resistance does notexceed the gain from additional devices, efficiency can be gained byadding more devices with a thickness more than 5-10 scattering lengths.This approach is described in Patent No. U.S. Pat. No. 6,396,191 B1 withless detail on a separate device. Ideally, barriers in each device or atleast a block of devices should be adjusted to operating temperature incompliance with formula (2). Multiple devices in series can be formedwith emitter injection barrier-only, emitter and collector injectionbarriers, emitter and collector blocking barriers, or all three barrierssimultaneously.

For example, FIG. 10A is a schematic depiction of a thermal diodeconverter of the invention that includes an emitter injectionbarrier-only stack 100 having a first diode 110 with a design structureof n*/p/n on the hot side (T_(H)), and a plurality of repeating N diodes120 of the same structure as first diode 110 that terminate on the coldside (T_(C)) with an n* layer. FIG. 10B is a schematic depiction of athermal diode converter of the invention that includes an emitterbarrier plus compensated layer (collector blocking barrier) stack 200.The stack 200 has a first diode 210 with a design structure ofn*/p/n/p_(c) on the hot side (T_(H)), and repeating N diodes 220 of thesame structure that end on the cold side (T_(C)) with an n* layer. FIG.10C is a schematic depiction of another thermal diode converter of theinvention that includes an emitter barrier plus collector injectionbarrier stack 300. The stack 300 has a first diode 310 with a designstructure of n*/p/n/p_(i) on the hot side (T_(H)), and repeating Ndiodes 320 of the same structure that end on the cold side (T_(C)) withan n* layer.

In addition, a thermal diode converter of the invention can also includean emitter barrier plus compensated layer and collector injectionbarrier stack. This stack has a first diode with a design structure ofn*/p/n/p_(i)/p_(c) similar to the diode shown in FIG. 1, and repeating Ndiodes having the same structure as the first diode that terminate withan n* layer as shown in FIGS. 10A-10C.

There are few ways of representing injection barrier. One is thatpotential barrier stops all carriers with energies below the barrierheight. Carriers that go over the barrier constitute a majority of theforward moving carriers and at a scattering length distance from thebarrier, effective carrier temperature is higher than the barrierheight. For a 100 meV barrier it is roughly 1200 K, with some dilutionfrom a Fermi-distribution in this layer. Assuming linear device behaviorin every aspect, the barrier can be regarded as a thermoelectric layerof the same material, but with a Seebeck coefficient four times higherthan at room temperature, or a figure of merit sixteen times highercompared with the same layer but without a barrier.

After a few scattering lengths carriers are in a thermal equilibriumagain and the barrier injection can be repeated. Unlike a stack of twothermoelectric plates, though, the next device in series will contributean equivalent Seebeck coefficient, which is more a function of barrierheight than interface temperature and can be close to the first device.A stack of two devices now has nearly double the Seebeck coefficient anddouble the thermal and electric resistance, but because figure of meritgoes up like the Seebeck coefficient squared, equivalent figure of meritgoes up.

In a 0.5 mm thick device, about 50-60 barrier structures can beaccommodated. In reality, contact resistance on each interface willreduce the heat flow through the device and injection current is part ofthe total heat flow, so the effect magnitude relative to thermoelectriceffect will go down. Simple modeling, assuming linear dependence of opencircuit voltage on temperature, shows that with ideal contactscontributing only phonon mismatch components to the contact thermalresistance, the optimum number of interfaces is about 20 with a 25 timesgain in a figure of merit. After about 100 interfaces there is no gain.A more complicated stack can include temperature adjusted barriers andthe like.

The designs shown in FIGS. 10A-10C are very useful for refrigerationapplications, because equivalent Peltier coefficient is proportional tothe sum of separate barrier heights. Coefficient of performance isproportional to the square of the Peltier coefficient and even a fewbarriers will result in a much better refrigeration performance.

As already mentioned above, after about 5-10 scattering lengths, gapdoes not contribute much to the device performance. This means that mostof the semiconductor material thickness can be replaced with a metal. Ametal layer in this case is used to reduce specific heat flow. Thedevice can be built by depositing emitter and collector semiconductorstructures as described above on a metal plate. The metal should bematched to the semiconductor in terms of thermal expansion coefficients.In some cases a thin intermediate amorphous layer of a semiconductor maybe necessary between the metal and emitter and collector structures. Fora p-type converter, a metal gap is more problematic, because reliableohmic contacts are required.

The present invention may be embodied in other specific forms withoutdeparting from its spirit or essential characteristics. The describedembodiments are to be considered in all respects only as illustrativeand not restrictive. The scope of the invention is, therefore, indicatedby the appended claims rather than by the foregoing description. Allchanges which come within the meaning and range of equivalency of theclaims are to be embraced within their scope.

1. A solid state energy converter with n-type conductivity, comprising:an emitter region in thermal communication with a hot heat exchangesurface, the emitter region comprising an n-type region with donorconcentration n* for electron emission; a p-type barrier layer withacceptor concentration p* in contact with the emitter region; and asegmented gap region in contact with the p-type barrier layer andcomprising a first layer of an n-type semiconductor material, and asecond layer of a metal, the second layer reducing heat flow density,wherein the p-type barrier layer provides a potential barrier and aFermi level discontinuity between the emitter region and the segmentedgap region.
 2. The solid state energy converter of claim 1, furthercomprising a collector region in thermal communication with a cold heatexchange surface, the collector region being in electrical and thermalcommunication with the gap region.
 3. The solid state energy converterof claim 2, wherein the gap region is adjacent to the collector region.4. The solid state energy converter of claim 2, further comprising afirst ohmic contact in electrical communication with the emitter region.5. The solid state energy converter of claim 4, further comprising asecond ohmic contact in electrical communication with the collectorregion.
 6. The solid state energy converter of claim 5, wherein thefirst and second ohmic contacts close an electrical circuit through anexternal load for heat to electricity conversion.
 7. The solid stateenergy converter of claim 5, wherein the first and second ohmic contactsclose an electrical circuit through an external power source forelectricity to refrigeration conversion.
 8. The solid state energyconverter of claim 1, wherein the p* doping concentration of the p-typebarrier layer relates to the n doping concentration of the gap region asp_(i)>n_(i)(m*_(p)/m*_(n)), where m*_(p) is the effective mass of holes,m*_(n) is the effective mass of electrons, and subscript i denotesionized fraction of carriers at a given temperature.
 9. The solid stateenergy converter of claim 2, wherein the collector region comprises anadditional injection barrier layer with a carrier concentration p** thatis adjacent to the gap region to reduce a thermoelectric back flowcomponent.
 10. The solid state energy converter of claim 2, wherein thecollector region comprises an additional compensation layer withacceptor concentration p* serving as a blocking layer at a cold side ofthe converter, and the acceptor concentration p* being the same as thedonor concentration in the gap region.
 11. The solid state energyconverter of claim 2, wherein the collector region comprises two p-typelayers, one layer with a carrier concentration p* serving as a blockinglayer at a cold side of the converter, and the other layer with acarrier concentration p** serving as an additional injection barrierlayer and being adjacent to the gap region to reduce a thermoelectricback flow component.
 12. The solid state energy converter of claim 11,wherein the p** doping concentration of the additional injection barrierlayer relates to the n doping concentration of the gap region asp_(i)>n_(i)(m*_(p)/m*_(n)), where m*_(p) is the effective mass of holes,m*_(n) is the effective mass of electrons, and subscript i denotesionized fraction of carriers at a given temperature.
 13. The solid stateenergy converter of claim 1, further comprising a first ohmic contact inelectrical communication with the emitter region and a second ohmiccontact in electrical communication with the gap region.
 14. The solidstate energy converter of claim 1, wherein the first layer is at least 1electron scattering length wide.
 15. The solid state energy converter ofclaim 1, wherein the first layer is at least 5 electron scatteringlengths wide.
 16. A solid state energy converter with p-typeconductivity, comprising: an emitter region in thermal communicationwith a hot heat exchange surface, the emitter region comprising a p-typeregion with acceptor concentration p* for hole emission; a semiconductorgap region with an acceptor doping p, the gap region in electrical andthermal communication with the emitter region, wherein the gap region issegmented and comprises a first layer of an p-type semiconductormaterial and a second layer of a metal; and an n-type barrier layer withdonor concentration n* in contact with the emitter region and with thegap region, the n-type barrier layer providing a potential barrier andFermi-level discontinuity between the emitter region and the gap region.17. The solid state energy converter of claim 16, further comprising acollector region in thermal communication with a cold heat exchangesurface, the collector region being in electrical and thermalcommunication with the gap region.
 18. The solid state energy converterof claim 17, wherein the gap region is adjacent to the collector region.19. The solid state energy converter of claim 18, further comprising afirst ohmic contact in electrical communication with the emitter region.20. The solid state energy converter of claim 19, further comprising asecond ohmic contact in electrical communication with the collectorregion.
 21. The solid state energy converter of claim 20, wherein thefirst and second ohmic contacts close an electrical circuit through anexternal load for heat to electricity conversion.
 22. The solid stateenergy converter of claim 21, wherein the first and second ohmiccontacts close an electrical circuit through an external power sourcefor electricity to refrigeration conversion.
 23. The solid state energyconverter of claim 16, wherein the gap region is at least 1 carrierscattering length wide.
 24. The solid state energy converter of claim16, wherein the gap region is at least 5 carrier scattering lengthswide.
 25. A solid state energy converter, comprising: a thermal diodestack comprising: a first diode with a design structure of n*/p/n on ahot side of the converter, the n* representing a n-type emitter regionwith a donor concentration n*, the p representing a p-type barrierregion with an acceptor concentration p, and the n representing a n-typesegmented gap region with a donor concentration n and comprising a firstlayer of an n-type semiconductor material and a second layer of a metal,wherein the barrier layer is configured to provide a potential barrierand Fermi-level discontinuity between the emitter region and the gapregion; a plurality of diodes having the same structure as the firstdiode and connected with the first diode; and an n* layer thatterminates the plurality of diodes on a cold side of the converter with.